Motor fuel



U ted t tes P fi 2, 15,145 r t a MoToRrUEL Weldon Annable, Mundelein, and William L. Jacobs and Robert Haines, 'CrystalLake, Ill., assignors to 511]? Pure Oil Company, Chicago, Ill a corporation of o i No Drawing. Application August 24, 1956 Serial No. 605,950 r r 9 Claims. (Cl. 208-917) This invention relates to gasoline-type motor fuels. It is more directly concerned with improving the cleanliness characteristics of gasolines.

In the operation of high-speed, high-output, sparkignited, internal combustion engines, conditions are conducive for the formation of intake or induction system deposits which interfere with the efliciency of the engines when employed as prime movers for automotive 'instal deasphalted, Mid-Continent lubricating oil distillate havburning of the intake refining processes used in the refining engineering, e. g., Petroleum Refining Engineer ing, Nelson, 3rd ed., McGraw-Hill; Modern Methods'of Refining Lubricating Oils, Kalichevsky, ACS Monograph #76, Reinhold. Because solvent extract fractions have inherent plasticizing characteristics, their use hasbeen suggested for overcoming resin and varnishdeposits which accumulate in the fuel induction system of an automotive engine, e. g., U. S. Patent 2,247,476: While a solvent extract fraction may have the property of mitigating the deposition of foreign accumulations in the cooler section of the induction system, c. g., intake manifold, a more critical scrutiny of the induction system shows that the deposits have merely moved from the cooler section to the hotter section and are formed around the intake valve port, stem, and tulip. According to this invention it has been found, however, that this disadvantageous effect can be ameliorated and induction system deposits substantially reduced by subjecting the extract fraction to mild treatment with hydrogen.

, The instant invention Will be more fully understood from the following detailed specific example of the prepa ficially modify the deposit-forming tendencies of gasoline.

It is another object of this invention to provide a motor fuel additive for mitigating the formation of induction System d p it f llzh. 1:. 1.2;

The formulationo'f "a full-boiling range gasoline generally employs as-the base fuel and as amajor constituent a cracked gasolinefproduced by the catalytic or non catalytic, thermal processing of petroleum gas-oil frac tions. Various types ofble'nding stocks such-as polymer gasoline,thermal-and catalytic ref ormate, Isomerate, alkylate, natural ga'soline,'*etc., are admixed therewithto supplementand/on complement the properties, such as octane number, vaporpress'ure, etc., of the base fuel. While the olefin-free constituents such' as *alkylate, Isomerate, catalytic reformate, and natural gasoline are sci-called clean burning? substances, the olefinic gasolines such as cracked gasolines, thermalreformate, and polymer gasolines contain unstable materials which are relativelyreactive and produce induction system deposits when employed in modern, high-speed, high-output, sparkignited, internal combustion engines?" According to this invention, it has" been foundthat'the formation of de posits in the induction system from unstable materials of this nature is reduced by'incorporatingsmall amounts of a hydrogen-treated, solvent extract obtained from the solvent refining of lubricating oils. 1]

The solvent extract ..;fractions which, are hydrogen was contacted in'aconventional"solventilrefinin pro ration and use of hydrogen-treated solvent extract. A

in g the vfollowing characteristics:

API gravity 27.5 SUS vis. 100 F 91.5 SUS visl. 210 F 38.0 Viscosity index, 63 Color, NPA}.-, +1V2 Carbon residue, (Ramsbottom) 0.06 Flash, COC, l

s. with phenol at a temperatllre of about ing 2.5 parts 'of phenol per lpart of charge stockflln producing ani vis. 100 F., V. I., neutral lubrieating oil asrafiinate, an extract material having the fo1lowingfproperties was obtainedi Physical: r 3

API gravity Specific grav., 60 F 0.951 Pounds/gallon 7.919. SUS viscosity- L F.. 65.5. F .833 t I 210 F 41 1 NPA color 8+, jFlash, F 375, 1 Fire, F

Pour, F

Total sulfur, wt. percent- Neutralization va1ue Chemical: U

Percent aromatics. Percent asphaltenes Aniline point, F u Rostler analysis z c u u 1 Percent nitrogen bases' Percent group 1 acidiffins Percent group 2 aciditfins Percent saturatedhydrocarbons-a 1 1.8: E, Chem. 43 (3) 598.

production of lubricating 011s are described in various standard works on petroleum Air-fuel ratio s DISTILLATION RANGE Tempera- Pereent Distilled ture F.

In the demerit rating system used on the'Lauson test the reference fuel is given a rating of twenty total points. This provides a value of 5 for normal deposits on engine parts and lighter deposits receive lower ratings, with for clean parts. Heavier than normal deposits are demerited by increasing the rating in steps of which will overshadow any clean engine part ratings and result in a greater than normal total rating.

In Table 1 is summarized the test results obtained by means of the Lauson test which clearly demonstrate the advantages that are obtained in mitigating induction system deposits. In interpreting the data, increased weights and increased ratings denote adverse results. The hydrogen-treated extract and untreated extract were prepared in accordance with the foregoing example;

Table l LAUSON TEST RESULTS Manit. Engine Numerical Rating Fuel Run No. Deposits, I

' Gms.

Port Stem Tulip Chamber Total 13842 1032 2 2 3 5 12 Regular Gasoline 1146 2 2 2 5 n 1210 .1464 2 2 2 5 11 Average .1214 2 2 2 5 '11 B843 .018 5 5 5 25 Regular Gasoline, 10 mL/gal. solvent extract 1211 .044 5 4 5 5 1!), fraction 1212 .017 4 '4. 10 5 28v 1213 .026 5 4 5 5 10 Average 026 5 4 8 5 22 B544 3 3 4 5 Regular Gasoline, 10 ml./gal. I'Iydrogen- 1214 .020 3 2 3 5 13 treated solvent extract 1215 .044 5 2 3 5 15 I 1216 .022 5 2 3 5 15 Average 028 4 2 3 5 l4 1 A conventional gasoline motor fuel containing 80 vol. of olefinic gasolines to provide a composition having the following properties:

API Gravity 61. 5 ASTM Distillation Range 10 percent 135 F 50 percent.. 215 F 90 percent 325 F prising molybdenum oxide supported on an alumina carrier. The product had the following characteristics:

Gravity, -API 19.3 Refractive index, N 1.5275 'Refractivity intercept n /ZDE" 1.0602 Color, ASTM (.NPA) 3 Total'sulfur, wt. percent 1.43 Neutralization value O.03

' The deposit-forming tendencies of gasolines containing a major portion of ,an olefinie gasoline were evaluated utilizing a Lauson H-2 single cylinder engine. The engine was equipped with a heated tubular glass manifold section maintained at 125 F. Temperatures were measured on the outside of the tube by an unshielded thermocouple. Current input to the heater generally was around 2 amperes. Intake manifold deposits were accumulated during .a 12-hour run employing the following engine operating conditions:

. l3 .8 Dynamornet'er load-watts 500 R. P. M 1500 Jacket temp., F 212 Manifold temp interior, F. 165 Manifold temp., exterior, F 315 Sump temp., F Q 140 Carburetor air temp., F 100 Fuel consumption, cc./min l0 After each test, the manifold was removed from the engine, and the amount of the manifold deposits determined by weighing the manifold on a suitable balance.

The engine numerical rating was; determined by visually evaluating the condition of intake systern, comprising the intake valve port, intake valve stem, intake valve tulip, and combustion chamber. I

From this it is seen that while untreated as well as hydrogen-treated solvent extract were instrumental in reducing the manifold deposits by -80%, the untreated solvent extract fraction had a severe deleterious effect, on the engine numerical rating. While a slight increase-in the engine numerical rating occurs when the hydrogen-treatedsolvent extract is incorporated in the gasoline, it is still well under the rating obtained using the untreated solvent extract fraction and comparablewith the, untreated solvent extract fraction-free gasoline. I

For the purposes of this invention, the solvent extract fraction which is hydrogen-treated to provide the induction system deposit-inhibitor of this invention isthat aromatic hydrocarbon-containing fraction obtained in the solvent refining processing of a petroleum oil fraction with a selective solvent to produce a mineral lubricating. oil of substantially improved V. I. and increased resistance to oxidation. Because of the factors involved in refining oils with selective solvents to producea rafiinate fraction of a desired quality, the properties of extract fractions will vary somewhatdepending upon the feed stock, solvent, and conditions.

The solvent extract fractions which are hydrogentreated to produce. the gasolineadditive of this invention will have an aromatic hydrocarbon content of about 70 to by weight, a boilingrang'e of 600 800? 11, 511! API gravity in the range of 10--20, and a refractivityintercept (J. F. 1., November 1936, page 563) of; not less than. 1.0525. In producing solvent extract fractions having these characteristics, lubricating oil stocks obtained from Pennsylvania, Mid-Continent, Gulf Coast andother crude petroleum oil source's can be used, although Mid-Continent or Gulf Coast crudes'v are preferred be-, cause they are more aromatic in. nature. Generally, solvent-to-oil ratiosiof. 1 to3 to 1 will produce extracts of desired properties; however, the selected ratio used w ll Table 11 PHYSICAL PROPERTIES OF SOLVENT EXTRACT FRAC- TIONS SUITABLE FOR HYDROGEN TREATING Light Medium Bright Neutral Neutral Stock API Gray ..r 17.3 10.8 14.0 SUS Vis. 100 F 165. 1327 27, 000 SUS Vis. 210 F 41. 1 65 360 N PA Color 3 Dilute +3 Dil 5 Dil. 375 415 530 430 490 595 +35 1 +35 +65 75 a5 90 695 730 mostly 709 795 above 727 835 900"1 The hycltotreating conditions employed are? H Itan ge Preferred Temperature, F 500-950 600 Pressure, p.s.i.; H 1100-500 250 Hydrogen rate, S. G. F. Hz/bl) 3005,000 2, 200 Liquid Volume Hourly Space Velocit 1-10 2. O

Mllder temperature conditions'are used when hydrogentreating the solvent extract fraction. obtained from the manufacture of low and medium viscosity, neutral, petroleum lubricating oils. The extract fractions obtained from the manufacture of high viscosity neutrals and bright stock are too heavy for best results and consequently must be cracked under mild conditions to reduce the average molecular weight. This may be done while hydrotreating by operating under more severe conditions,

that is, at higher temperatures. Other conditions are essentially the same but the temperature is raised to the range of 825950 F., preferably 875 F. Although the hydrofining conditions do not reduce the sulfur content appreciably, there is, nevertheless, some reduction of sulfur by decomposition to hydrogen sulfide. The hydrofined product must be stripped free of hydrogen sulfide. To promote the efliciency of the reaction, typical prior art hydrogenation catalysts can be employed. Hydrogenation catalysts comprising oxides or sulfides of groups VI and VIII metals are particularly useful, e. g., nickel, cobalt and iron as metals or oxides, nickel tungstate, cobalt molybdate, chromium, molybdenum and tungsten oxides or sulfides, etc. The catalysts are preferably distributed on or incorporated in a porous carrier such as activated alumina, silica gel, various siliceous cracking catalysts including SiO -Al O SiO ZrO etc. In the course of hydrogen-treating these conventional hydrogenation catalysts will lower the neutralization value of the solvent extract fraction. To obtain optimum results it is preferred that hydrogenation catalysts be used which will reduce the neutralization no. (1948) to. less than 0.5 as a concomitant result in the hydrogen treating of the solvent extract fraction feed. Best results are obtained when the hydrogen-treated solvent extract have a neutralization value (1948) of less than 0.03. Specific conventional hydrogenation catalysts which will effect this maximum reduction include: M00 on alumina where the alumina is prepared from aluminum sulfate in a conventional manner, nickel molybdate on alumina and silver molybdate on alumina, and others which function in this manner.

e The amount of hydrogen-treated extract fraction to be used. will vary, depending upon the amount of olefinic gasolines present in the finished motor fuel. Accordingly,

the optimum amount should be determined experimentally. In general, about 10 to 50#/1000 bbls., based on the total gasoline component of the finished fuel,-

should be employed; however, amounts outside this range can be used.

The gasoline-type motor fuels which are beneficiated in. accordance with this invention are those which contain' a substantial portion of olefinic distillates boiling in the. gasoline range. In general, amounts between about S to 100 vol. percent of a gasoline, such as those prepared by the catalytic, or non-catalytic, thermal decomposition of a petroleum gas oil fraction; non-catalytic, thermal reforming of light petroleum distillates; of

or polymerization olefinic gases, in the finished gasoline, produce undesirable induction system deposits. As has been pointedout above, other hydrocarbon blending components can t be admixed with the cracked base stock; In addition,

the compounded gasolines can contain other additives such as tetraethyl lead fiuid,ignition. improvers such as organicphosphates, esters of dibasic organic acids, antioxidants, etc. These additives can also contribute to the induction system deposit-forming tendencies of the base gasoline, a deleterious result which is also mitigated by, the use of the hydrogen-treated solvent extract of this.

invention.

. Although the instant invention has been illustrated by specific compositions which carry out the objectives of,

this invention, it is obvious that variations will be apparent to those skilled in the art to which this invention pertains.

invention as;

1. A gasoline motor fuel composition comprising a portion of an olefinic gasoline having induction system deposit-forming tendencies and an amount sufiicient to mitigate the accumulation of inductionsystem deposits of a hydrogen-treated solvent extract, said hydrogentreated solvent extract being prepared by contacting a solvent extract fraction, obtained from the solvent refining of a lubricating oil stock with a selective solvent to produce a lubricating oil having an enhanced viscosity index and improved resistance to oxidation, with hydrogen at a temperature of about 600950 F., a pressure of about -500 p. s. i., a hydrogen rate of about 300- 5000 s. c. f. hydrogen/ barrel of feed, and a liquid hourly volume space velocity of about 0.5-10.0 in the presence of a hydrogenation catalyst.

2. A motor fuel composition in accordance with claim 1 in which the gasoline portion of said composition contains 5100 volume percent of an olefinic gasoline.

3. A motor fuel composition in accordance with claim 1 in which said solvent extract fraction is obtained from the manufacture of neutral petroleum lubricating oils with a selective solvent.

4. A gasoline motor fuel composition comprising a gasoline base containing 5-100 volume percent of an olefinic gasoline having incorporated therein an amount of an hydrogen-treated, solvent extract fraction sufiicient to mitigate the accumulation of induction system deposits, said hydrogen-treated solvent extract being prepared by contacting a solvent extract fraction containing 70-90 wt. percent of aromatic hydrocarbons, said fraction being obtained from the solvent refining of a petroleum lubricating stock with a selective solvent to produce a lubricating oil having an enhanced V. I. and improved resistance to oxidation, with hydrogen at a temperature of about 600-950 F., a pressure of about 100-500 p. s. i., a hydrogen rate of about 300-5000 s. c. f. hydrogen/ barrel of feed, and a liquid hourly volume space velocity of about 0.5-10.0 in the presence ofa hydrogenation Accordingly, the invention is limited only by the appended claims which define andclaim the subject asp-alga induction system deposits.

6. A composition in accordance with claim 4 in which said hydrogentreated extract has a neutralization value ofless than about 015l- '7 A gasoline motor 'fuel composition comprising a gasoline base containing 5-100 volume percent of a cracked gasoline having induction system deposit-forming tendencies having incorporated therein -50 pounds per one thousand barrels of gasoline base of a hydrogentreated 'solvent extract'having a neutralization value of less than 0.3 to mitigate the accumulation of induction system deposits, saidhydrogen-treated solvent extract being prepared by contacting a solvent extract fraction" obtained: from solvent refining of a lubricating oil stock to produce a lubricatingoil having enhanced viscosity index and improved oxidation resistance, having the followingcharacteristics; ASTM boiling range (10%- 90%-) of 69572 7 F., API gravity*l6.9, 73.2 Wt. percent aromatics, said fraction being obtained fromthe manufacture of'a Mid-Continent neutral petroleum lubricating oil, With hydrogen at a temperature of about 750 F., a pressure of about 500 p. s. i. g., a liquid hourly space velocity of 2.2 anda hydrogen rate of about 2500 ft.

cu./barrel -(STP) in the presence of a hydrogenation catalyst comprising 9% molybdenum oxide supported on an alumina carrier.

i 8. A gasoline, motor fuel additive comprising a hydrogen-treateisolvent extract prepared by contacting a solvent extract'fraction having an ASTM boiling range of 600-950 R, an API gravity 0f10-20 API, an arorhatic hydrocarbon content of about 70-95% by Weight and a refractivity intercept of not less than about 1.0525,

obtained from the solvent refining of a lubricating oil stock with a selective solvent to produce a lubricating oil'having an enhanced'viscosity index and improved re-J sjistance to oxidation, with hydrogen at-a temperature of about 600-950 F a pressure of about 100-500 p'. s."i.,' a hydrogen rateof about 300-5000 s. c. f. hydrogeri/ barrelof feed, and a liquid hourly volume space velocity of about 05-100 in the presence of a hydrogenation catalyst.

9. A gasoline, motor fuel additive comprising a hydrogen-treated, solvent extract having a neutralization value (ASTM Designation D974-52T) of not more than 0.03 prepared by contacting a solvent extract fraction having anASTM boiling range of'600-950' F., an'API gravity of 10-20 API, an aromatic hydrocarboncontent of about -95% by weight and a refractivity intercept of not less than about 1.0525, obtained from the solvent refining of a lubricating oil stock with a selective solvent to produce a lubricating oil having an enhanced viscosity index and improved resistance to oxidation, with hydrogen at a temperature of about 600-950 F. a pres sure of about -500 p. s. i., a hydrogen rate of about 300-5000 s. c. f. hydrogen/barrel of feed, and a liquid hourly volume space velocity of about 05-100 in the presence of a hydrogenation catalyst selected from the group consisting of molybdena on alumina, nickel molybdate on alumina, and silver molybdate on alumina.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A GASOLINE MOTOR FUEL COMPOSITION COMPRISING A PORTION OF AN OLEFINIC GASOLINE HAVING INDUCTION SYSTEM DEPOSIT-FORMING TENDENCIES AND AN AMOUNT SUFFICIENT TO MITIGATE THE ACCUMULATION OF INDUCTION SYSTEM DEPOSITS OF A HYDROGEN-TREATED SOLVENT EXTRACT, SAID HYDROGENTREATED SOLVENT EXTRACT BEING PREPARED BY CONTACTING A SOLVENT EXTRACT FRACTION, OBTAINED FROM THE SOLVENT REFINING OF A LUBRICATING OIL STOCK WITH A SELECTIVE SOLVENT TO PRODUCE A LUBRICATING OIL STOCK WITH A SELECTIVE SOLVENT TO INDEX AND IMPROVE RESISTANCE TO OXIDATION, WITH HYDROGEN AT A TEMPERATURE OF ABOUT 600*-950*F., A PRESSURE OF ABOUT 100-500 P. S. I., A HYDROGEN RATE OF ABOUT 3005000 S. C. F. HYDROGEN/BARREL OF FEED, AND A LIQUID HOURLY VOLUME SPACE VELOCITY OF ABOUT 0.5-10.0 IN THE PRESENCE OF A HYDROGENATION CATALYST. 